Oral Presentation Royal Australian Chemical Institute National Congress 2026

Atmospheric fates and global warming potential of HFO-1234ze(E) and its degradation product trifluoroacetaldehyde CF3CHO (136626)

Beth Killen 1 , Jenny A. Fisher 2 3 , Christopher S. Hansen 1 , Scott H. Kable 1
  1. School of Chemistry, UNSW , Sydney, NSW, Australia
  2. College of Science and Engineering, James Cook University, Douglas, QLD, Australia
  3. Environmental Futures, University of Wollongong, Wollongong, NSW, Australia

Hydrofluoroolefins (HFOs) have been adopted as replacements for high-GWP hydrofluorocarbons (HFCs) across multiple applications including foam blowing, refrigeration, and aerosols, but their atmospheric degradation and climate consequences remain uncertain.1,2 Here, we use the GEOS-Chem 3-D chemical transport model, supported by AtChem2 box-model simulations, to develop a complete representation of the atmospheric chemistry and fate of HFO-1234ze(E) and its key intermediate product, CF3CHO. The model includes newly measured CF3CHO photolysis quantum yields to form fluoroform (HFC-23), the recently identified chemical pathways of HFO-1234ze(E) ozonolysis and CF3CHO reversible reaction with HO2, and explicit wet and dry deposition parameterisations.2,3 Using observationally constrained global HFO-1234ze(E) emissions of 35 Gg yr-1, simulated HFO-1234ze(E) surface mixing ratios agreed well with observations at 8 Advanced Global Atmospheric Gases Experiment (AGAGE) sites across the globe.4 We find that 99.6% of HFO-1234ze(E) is removed by reaction with OH, with the remaining 0.4% lost to ozonolysis. Sensitivity tests for effective Henry's law constants (KH*) spanning 10 - 106 M atm-1 show sensitivity of \ce{CF3CHO} fate to KH* up to 104 M atm-1 and saturation at higher KH*. Using an upper bound of 105 M atm-1, we find deposition accounts for about 55% of total CF3CHO loss in GEOS-Chem (17% dry, 38% wet), with a further 25% lost to photolysis and 17% to reaction with OH. The reversible reaction with HO2 contributes just 1% to net CF3CHO loss due to rapid conversion of the reaction products back to reactants.  We find an overall GWP100 for HFO-1234ze of around 13, with CF3CHO photolysis to HFC-23 contributing 5.4. We also estimate a maximum potential formation of 6 Gg yr-1 of trifluoroacetic acid (TFA) from wet-deposited CF3CHO, suggesting a potential unrecognised TFA source from atmospheric degradation of HFO-1234ze(E). 

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  2. B. Long, Y. Xia and D. G. Truhlar, Journal of the American Chemical Society, 2022, 144 (43), 19910-19920
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